JP2008111080A - Method of surface-treating fluorescent substance, fluorescent substance, fluorescent substance-containing composition, light emitting device, image display device, and illuminating device - Google Patents

Method of surface-treating fluorescent substance, fluorescent substance, fluorescent substance-containing composition, light emitting device, image display device, and illuminating device Download PDF

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JP2008111080A
JP2008111080A JP2006296239A JP2006296239A JP2008111080A JP 2008111080 A JP2008111080 A JP 2008111080A JP 2006296239 A JP2006296239 A JP 2006296239A JP 2006296239 A JP2006296239 A JP 2006296239A JP 2008111080 A JP2008111080 A JP 2008111080A
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phosphor
eu
light
sr
emitting device
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Eiji Hattori
Hiroshi Mori
Masato Niihara
Keiichi Seki
正人 新原
英次 服部
寛 森
敬一 関
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Mitsubishi Chemicals Corp
三菱化学株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321Disposition
    • H01L2224/32151Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
    • H01L2224/73265Layer and wire connectors

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor surface treatment method excellent in weather resistance and dispersibility, and a phosphor excellent in moisture resistance and dispersibility. In addition, a high-quality phosphor-containing composition, a light-emitting device, an image display device, and a lighting device using the phosphor are provided.
A phosphor surface treatment method comprising a step of hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof at an atmospheric temperature of 0 ° C. to 20 ° C. And / or a phosphor surface treatment method comprising a step of hydrolyzing and dehydrating and polymerizing a metal alkoxide and / or a derivative thereof twice or more. A phosphor having a metal oxide film, wherein the metal oxide film satisfies a predetermined condition.
[Selection figure] None

Description

  The present invention relates to a phosphor surface treatment method, a phosphor, a phosphor-containing composition, a light emitting device, an image display device, and an illumination device. Specifically, a phosphor surface treatment method excellent in weather resistance and dispersibility, a phosphor excellent in weather resistance and dispersibility, a phosphor-containing composition containing the phosphor, and the phosphor The present invention relates to a formed light emitting device, and an illumination device and an image display device formed using the light emitting device.

Conventionally, phosphors have been used industrially in large quantities for CRTs, fluorescent lamps, etc., but in these applications, a method of using them as aqueous slurries when applying phosphors has been established industrially. Deteriorating phosphors could not be used.
On the other hand, in recent years, a technology for producing a white light emitting device by converting the wavelength of light emitted from a semiconductor light emitting chip with a phosphor has been put into practical use. Unlike the aforementioned CRT and fluorescent lamp, the phosphor used here does not need to be an aqueous slurry in the manufacturing process. Therefore, if the light emission characteristics are excellent, even if some deterioration due to moisture is recognized, there is a case where there is no problem for short-term use by encapsulating the phosphor with the sealant.

However, for long-term use, there are many points that are insufficient in practicality, and countermeasures against deterioration of such phosphors due to moisture have been demanded.
Examples of the surface treatment method of the phosphor include a method of attaching spherical silicon oxide fine powder to the phosphor (Patent Literature 1, Patent Literature 2), a method of attaching a silicon compound film to the phosphor (Patent Literature 3), A method of coating the surface of phosphor fine particles with polymer fine particles (Patent Document 4) has been disclosed for a long time, and these have been aimed at improving the glass surface fog characteristics and the luminance of CRT phosphors. Therefore, the effect of improving the moisture resistance of the phosphor was not sufficient.

Also, for the purpose of improving the humidity resistance of the phosphor, a method of coating the phosphor with an organic material, an inorganic material, a glass material, etc. (Patent Document 5), and a method of coating the surface of the phosphor by a chemical vapor reaction method (Patent Document 6), a method of attaching metal compound particles (Patent Document 7), and the like are disclosed. However, further studies are necessary to improve the moisture resistance in long-term use.
Japanese Patent Laid-Open No. 2-209989 JP-A-2-233794 JP-A-3-231987 JP-A-6-314593 JP 2002-223008 A JP 2005-82788 A JP 2006-28458 A

  The present invention has been made in view of the above-described prior art, and is a phosphor that has low moisture resistance, imparts weather resistance such as moisture resistance to a phosphor that deteriorates due to moisture, and does not deteriorate over time even in the long term. The object is to provide a surface treatment method, a phosphor, a phosphor-containing composition, a light emitting device, an image display device, and a lighting device.

  Accordingly, the present inventors have made extensive studies and hydrolyzing and dehydrating and polymerizing metal alkoxide and / or its derivative at a relatively low temperature, and / or hydrolyzing metal alkoxide and / or its derivative. The inventors have found that the above-mentioned problems can be solved when the dehydration polymerization step is performed twice or more, thereby completing the present invention. Moreover, it discovered that the said subject was solved when a metal oxide film satisfy | fills specific conditions, and completed this invention. In addition, the phosphor manufactured by such a surface treatment method or the phosphor having the above-mentioned specific film characteristics is further excellent in dispersibility, and thus, for example, the dispersibility of the phosphor in the phosphor-containing resin portion of the light emitting device can be improved. I found out.

That is, the gist of the present invention resides in the following [1] to [8].
[1] A phosphor surface treatment method comprising a step of hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof at an atmospheric temperature of 0 ° C. or higher and 20 ° C. or lower.
[2] A phosphor surface treatment method comprising a step of hydrolyzing and dehydrating and polymerizing a metal alkoxide and / or a derivative thereof twice or more.
[3] A phosphor surface-treated by the phosphor surface treatment method according to [1] or [2]. [4] A phosphor having a metal oxide film, wherein the metal oxide film satisfies the following conditions (1) to (4).
(1) It is formed by hydrolysis and dehydration polymerization of a metal alkoxide and / or its derivative. (2) Substantially continuity is observed by a transmission electron microscope.
(3) The film thickness is 1 nm or more and 10,000 nm or less. (4) The moisture absorption increase rate measured by the moisture absorption measurement test according to the following (i) to (iii) is 5% by weight or less [Moisture absorption measurement test].
(I) The metal oxide film is formed on the orange phosphor Sr 2 BaSiO 5 : Eu (hereinafter abbreviated as SBS, weight median diameter D50 = 20 ± 3 μm) by an arbitrary method.
(Ii) Leave in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 100 hours.
(Iii) Moisture absorption increase rate (% by weight) = (weight after moisture absorption test−weight before moisture absorption test) / (weight before moisture absorption test) × 100.
[5] A phosphor-containing composition containing the phosphor according to [3] or [4].
[6] A light emitting device using the phosphor according to [3] or [4].
[7] An image display device using the light emitting device according to [6].
[8] An illumination device using the light emitting device according to [6].

The phosphor surface treatment method and the phosphor of the present invention have the following excellent effects.
(I) It is possible to further improve the weather resistance such as moisture resistance of the phosphor before the surface treatment (hereinafter also referred to as a base phosphor) which is the base of the phosphor of the present invention.
(Ii) Dispersibility of the phosphor-containing resin portion of the light-emitting device in the resin can be improved as compared with the base phosphor.

  In addition, since the phosphor-containing composition, the light emitting device, the image display device, and the lighting device of the present invention use the phosphor, the phosphor-containing composition has excellent long-term weather resistance and high quality.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
[1] Phosphor surface treatment method The phosphor surface treatment method of the first aspect of the present invention must include a step of hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof at an atmospheric temperature of 0 ° C. or higher and 20 ° C. or lower. (Claim 1).
The phosphor surface treatment method according to the second aspect of the present invention essentially includes the step of hydrolyzing and dehydrating and polymerizing the metal alkoxide and / or derivative thereof (claim 2).
Hereinafter, each component will be described in detail.

[1-1] Metal alkoxide and / or derivative thereof The metal alkoxide used in the present invention refers to a compound in which a metal is bonded to an alkoxyl group, and is generally represented by the general formula M (OR) n (M is a metal element, and R is an alkyl). Group, n represents the acid number of the metal element).

In the general formula, M is preferably Si, Ti, Zr, Nb, or V. Moreover, carbon number of the alkyl group of R becomes like this. Preferably it is 1-5, More preferably, it is 1-3.
Specific examples of the metal alkoxide used in the present invention include silicon alkoxides having 1 to 3 carbon atoms such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane because of their reactivity and availability on an industrial scale. Are preferably used.

Examples of the metal alkoxide derivative include a low condensate derivative obtained by partially hydrolyzing and polycondensing a metal alkoxide. Specific examples include low condensate derivatives obtained by partially hydrolyzing and polycondensing silicon alkoxides such as tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.
[1-2] Substrate phosphor The phosphor (substrate phosphor) to be subjected to the surface treatment method of the present invention is not particularly limited, but a phosphor having excellent light emission characteristics but low moisture resistance is not limited to the present invention. This surface treatment method is preferable because it can be preferably used for a light emitting device or the like. Specific examples of the base phosphor will be described later in section [2].

[1-3] Hydrolysis and dehydration polymerization step In the phosphor surface treatment method of the present invention, the step of hydrolyzing and dehydrating the metal alkoxide and / or its derivative is performed at a low temperature of from 0 ° C. to 20 ° C. (Hereinafter, sometimes referred to as “low temperature treatment”) and / or two or more times (hereinafter, sometimes referred to as “multiple treatment”). By performing such a process, a dense and strong film is formed on the base phosphor, and moisture resistance and dispersibility are improved. Details will be described below.
[1-3-1] Low-Temperature Treatment In the phosphor surface treatment method of the first aspect of the present invention, the step of hydrolyzing and dehydrating the metal alkoxide and / or derivative thereof is performed at a low temperature of from 0 ° C. to 20 ° C. . Thereby, a uniform continuous film can be formed on the surface of the base phosphor. The liquid temperature is preferably 0 ° C. or higher, more preferably 5 ° C. or higher. Moreover, Preferably it is 10 degrees C or less. If each solution does not solidify, the lower temperature is preferable for increasing the film thickness, but if the temperature is too low, a large amount of metal oxide precipitates locally and tends to form an uneven surface film, which is not preferable.
Specifically, for example, as described later in [1-4-3], a method in which a metal alkoxide solution and a base phosphor-containing solution are mixed at an ambient temperature of 0 ° C. or higher and 20 ° C. or lower can be exemplified.

[1-3-2] Multiple times treatment In the phosphor surface treatment method of the second aspect of the present invention, the step of hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof is performed twice or more. Thereby, the film once formed is covered with still another film, and a strong film can be formed. Further, it is possible to prevent the cracks generated in the first layer coating from being covered with the second layer coating and moisture from entering the phosphor. The number of treatments is preferably 3 times or more. When the number of treatments is increased, the moisture barrier property of the film increases accordingly, but as the number of treatments is repeated, the improvement in moisture barrier properties becomes smaller, so even if treatment is performed 5 times or more, there is little effect on labor. .
Specifically, as described later in [1-4-6], for example, a method of mixing a metal alkoxide solution and a base phosphor-containing solution, washing, and drying may be repeated a plurality of times.

[1-4] Treatment conditions The phosphor surface treatment method of the present invention is not particularly limited as long as it includes a step of hydrolyzing and dehydrating and polymerizing the metal alkoxide and / or derivative thereof. This is carried out through the steps (i) to (v). Hereinafter, each process is explained in full detail.
(I) a step of preparing a metal alkoxide solution (hereinafter abbreviated as TAOM solution) (ii) a step of preparing a substrate phosphor-containing solution (hereinafter abbreviated as PHOS solution) (iii) of (i) and (ii) above Mixing surface treatment step (iv) washing step (v) drying step of mixing the solution obtained in the step

[1-4-1] (i) Metal alkoxide solution (TAOM solution) preparation step The metal alkoxide is diluted with an organic solvent. As the organic solvent to be used, one or a mixture of two or more of alcohols, glycol derivatives, esters, ketones, ethers and the like can be used.
Among the solvents, alcohols are preferable and alcohols having 1 to 4 carbon atoms are more preferable from the viewpoint of adhesion of the film to the base phosphor. Specific examples include methanol, ethanol, isopropanol, and butanol. Of these, methanol and ethanol are preferable. The amount of the solvent is 200 parts by weight or more, preferably 400 parts by weight or more with respect to 100 parts by weight of the metal alkoxide.

  If the amount of the solvent is too small, a continuous film having a sufficient thickness may not be obtained on the surface of the base phosphor. That is, since the TAOM solution has a high concentration, when dropped in a PHOS solution containing ammonia water in the step [1-4-2] to be described later, the TAOM concentration locally increases, and the surface of the substrate phosphor is increased. It polymerizes before reaching, and a spherical metal oxide is produced exclusively in place of the film.

[1-4-2] (ii) Preparation process of substrate phosphor-containing solution (PHOS solution) The substrate phosphor is made into a slurry by adding an organic solvent, moisture necessary for hydrolysis and, if necessary, a catalyst for promoting hydrolysis. . As the organic solvent, those used for the metal alkoxide solution can be used as they are. As a catalyst for the hydrolysis reaction of metal alkoxide, for example, aqueous ammonia can be used. Furthermore, as a suitable example of the slurry, a substance obtained by dispersing the base phosphor in a solution obtained by adding aqueous ammonia to ethanol can be used. The amount of the substrate phosphor is not limited as long as it is sufficiently dispersed by stirring in the reaction solution. However, in the case of a substrate phosphor having a large specific gravity and particle size, the substrate phosphor settles in the reaction solution to form a film. Therefore, it is necessary to reduce the amount of the base phosphor and disperse it well in the reaction solution. From this point of view, the base phosphor is usually 1% by weight or more and 20% by weight or less with respect to the total reaction solution. Further, the ratio of the catalyst for hydrolysis is not particularly limited, but in order to suppress the formation of the spherical metal oxide in the reaction solution and activate the film formation, it is 5% by weight or more based on the total reaction solution. 20% by weight or less is preferable.

[1-4-3] (iii) Mixed surface treatment step The TAOM solution obtained in the step (i) is stirred while the PHOS solution obtained in the step (ii) is sufficiently stirred so that the base phosphor does not settle. It is dripped at a predetermined speed. The stirring speed of the PHOS solution varies depending on the particle size distribution and density of the phosphor, but it is preferable to stir at a speed that does not cause precipitation at the bottom of the container.
If the TAOM solution is added too quickly, the hydrolysis rate becomes too high and particles are formed and a film cannot be obtained. Therefore, the addition is usually 30 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer. It is preferable to carry out evenly.
The liquid temperature of the PHOS solution at the time of dropping is preferably low if each solution does not solidify in order to increase the film thickness. However, if the temperature is too low, a lot of metal oxide is locally deposited and uneven. Since it tends to be a surface film, it is usually 0 ° C. or higher and 20 ° C. or lower, preferably 10 ° C. or lower. The amount of the metal alkoxide used is usually 5% by weight or more, preferably 10% by weight or more, and usually 30% by weight or less, preferably in terms of the amount of the metal element, based on the weight of the phosphor to be treated. 20% by weight or less. If the amount of metal alkoxide used is too small, the formation of the film becomes insufficient and the continuity of the film is lost, so that sufficient moisture resistance may not be obtained. On the other hand, if the amount is too large, the film becomes too thick and cracks or peeling occurs, resulting in loss of continuity of the film, so that sufficient moisture resistance may not be obtained.

[1-4-4] (iv) Washing Step The mixed solution obtained in the step (iii) is allowed to stand, and the spherical metal oxide or the like that has not become a film is removed together with the supernatant. Next, a solvent such as alcohol is added, and the mixture is left to stand after stirring, and the supernatant is discarded. After repeating this washing operation several times, solid-liquid separation is performed by a method such as decantation, filtration or centrifugation. The number of repetitions of washing is usually 2 times or more, preferably 3 times or more. There is no limit to the number of repetitions, but there is no need to repeat the cleaning process if the cleaning liquid becomes transparent.

[1-4-5] (v) Drying step The cake obtained in (iv) is dried under reduced pressure in a vacuum dryer having a heating device. For example,
The initial 30 minutes may be heated to 50 ° C., then heated to 150 ° C. and held for 2 hours.
[1-4-6] Coating treatment When the coating amount of the obtained phosphor does not reach the desired amount, a phosphor-containing solution is prepared again with the obtained phosphor, and the above (iii) step and the subsequent steps May be repeated.

  In particular, in the drying step [1-4-5] described above, if the film is dried too quickly, cracks may be formed in the film, and moisture may enter from the cracks to deteriorate the phosphor. Absent. In that case, by repeating the steps [1-4-1] to [1-4-5] described above, the film once formed can be covered with still another film. It is possible to prevent the cracks generated in the first layer film from being covered with the second layer film and moisture from entering the phosphor. In this case, a crack may be formed in the coating of the second layer. This is because moisture intrusion through the crack does not reach the phosphor unless the first layer and the second layer are accidentally communicated.

Further, after the above-described [1-4-4] cleaning step, the steps [1-4-1] to [1-4-5] are performed to increase the film thickness, thereby It is also possible to further improve the moisture resistance.
[2] Phosphor The phosphor according to the first aspect of the present invention is a phosphor that has been surface-treated by the above-described phosphor surface treatment method (claim 3).
The phosphor of the second aspect of the present invention is a phosphor having a metal oxide film, wherein the metal oxide film satisfies the following conditions (1) to (4) ( Claim 4).
(1) It is formed by hydrolysis and dehydration polymerization of a metal alkoxide and / or its derivative. (2) Substantially continuity is observed by a transmission electron microscope.
(3) The film thickness is 1 nm or more and 10,000 nm or less. (4) The moisture absorption increase rate measured by the moisture absorption measurement test according to the following (i) to (iii) is 5% by weight or less.

[Moisture absorption measurement test]
(I) The metal oxide film is formed on the orange phosphor Sr 2 BaSiO 5 : Eu (hereinafter abbreviated as SBS, weight median diameter D50 = 20 ± 3 μm) by an arbitrary method.
(Ii) Leave in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 100 hours.
(Iii) Moisture absorption increase rate (% by weight) = (weight after moisture absorption test−weight before moisture absorption test) / (weight before moisture absorption test) × 100.
Hereinafter, each component will be described in detail.

[2-1] Base phosphor The effects of the phosphor surface treatment methods according to the first and second aspects of the present invention are suitably exerted on a phosphor that easily reacts with moisture from the viewpoint of improving water resistance.
[2-1-1] Phosphor that easily reacts with moisture As the phosphor that becomes the base of the phosphor of the present invention, that is, the phosphor that easily reacts with moisture that becomes the base phosphor, inorganic phosphors and organic phosphors are included. Can be mentioned.

As the inorganic phosphor, for example, a group consisting of M 3 SiO 5 , MS, MGa 2 S 4 , MAlSiN 3 , M 2 Si 5 N 8 , MSi 2 N 2 O 2 as a base crystal (where M is Ca, Sr , Ba represents at least one selected from the group consisting of Ba, and an activator is Cr, Mn, Fe, Bi, Ce, Pr, Nd, Sm, Eu, Tb. , Dy, Ho, Er, Tm, and a phosphor containing at least one of Yb.

As a specific example of the phosphor, for example,
Ba 3 SiO 5 : Eu, (Sr 1-a Ba a ) 3 SiO 5 : Eu, Sr 3 SiO 5 : Eu
,
CaS: Eu, SrS: Eu, BaS: Eu, CaS: Ce, SrS: Ce, BaS: Ce,
CaGa 2 S 4: Eu, SrGa 2 S 4: Eu, BaGa 2 S 4: Eu, CaGa 2 S 4: Ce, SrGa 2 S 4: Ce, BaGa 2 S 4: Ce,
CaAlSiN 3 : Eu, SrAlSiN 3 : Eu, (Ca 1-a Sr a ) AlSiN 3 :
Eu, CaAlSiN 3 : Ce, SrAlSiN 3 : Ce, (Ca 1-a Sr a ) AlSi
N 3 : Ce,
Ca 2 Si 5 N 8: Eu , Sr 2 Si 5 N 8: Eu, Ba 2 Si 5 N 8: Eu, (Ca 1-a Sr a) 2 Si 5 N 8: Eu, Ca 2 Si 5 N 8: Ce, Sr 2 Si 5 N 8 : Ce, B
a 2 Si 5 N 8: Ce , (Ca 1-a Sr a) 2 Si 5 N 8: Ce,
CaSi 2 N 2 O 2 : Eu, SrSi 2 N 2 O 2 : Eu, BaSi 2 N 2 O 2 : Eu, CaSi 2 N 2 O 2 : Ce, SrSi 2 N 2 O 2 : Ce, BaSi 2 N 2 O 2 : Ce
(With respect to the above, a satisfies 0 ≦ a ≦ 1).
Among them, Sr 2 BaSiO 5 : Eu, CaS, CaGa 2 S 4 : Eu, SrGa 2 S 4 : Eu, (Sr 0.8 Ca 0.2 ) AlSiN 3 : Eu, and SrAlSiN 3 : Eu are preferable. I can do it.

[2-1-2] Other phosphors In addition to phosphors that easily react with moisture, other phosphors can be used as the base phosphor depending on the purpose, such as improved durability and improved dispersibility. .
The composition of such a base phosphor is not particularly limited, but a metal oxide typified by Y 2 O 3 , Zn 2 SiO 4, etc., which is a crystal matrix, and a metal nitride typified by Sr 2 Si 5 N 8, etc. , Ca 5 (
PO 4 ) 3 Cl etc. and phosphates such as ZnS, SrS, CaS etc., Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, A combination of rare earth metal ions such as Yb and metal ions such as Ag, Cu, Au, Al, Mn, and Sb as activators or coactivators is preferred.
Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa 2 S 4 , SrS, and ZnS, oxysulfides such as Y 2 O 2 S, and (Y, Gd) 3 Al 5 O. 12 , YAlO 3 , BaMgAl 10 O 17 , (Ba, Sr) (Mg, Mn) Al 10 O 17 , (Ba, Sr, C
a) (Mg, Zn, Mn) Al 10 O 17 , BaAl 12 O 19 , CeMgAl 11 O 19
, (Ba, Sr, Mg) O.Al 2 O 3 , BaAl 2 Si 2 O 8 , SrAl 2 O 4 , Sr 4 Al 14 O 25 , Y 3 Al 5 O 12, etc., aluminates such as Y 2 SiO 5 Silicate such as Zn 2 SiO 4 , oxide such as SnO 2 and Y 2 O 3 , borate such as GdMgB 5 O 10 and (Y, Gd) BO 3 , Ca 10 (PO 4 ) 6 (F, Cl ) 2 , halophosphates such as (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 , phosphates such as Sr 2 P 2 O 7 , (La, Ce) PO 4, etc. it can.

However, the crystal matrix and the activator element or coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following can be used as the base phosphor, but these are merely examples, and the base phosphor that can be used in the present invention is not limited thereto. In the following examples, base phosphors that differ only in part of the structure are omitted as appropriate. For example, “Y 2 SiO 5 : Ce 3+ ”, “Y 2 SiO 5 : Tb 3+ ” and “Y 2 SiO 5 : Ce 3+ , Tb 3+ ” are changed to “Y 2 SiO 5 : Ce 3+ , Tb 3+ ”, “ “La 2 O 2 S: Eu”, “Y 2 O 2 S: Eu” and “(La, Y) 2 O 2 S: Eu” are collectively shown as “(La, Y) 2 O 2 S: Eu”. ing. Omitted parts are shown separated by commas (,).

[2-1-2-1] Orange to red phosphor
Examples of the base phosphor that emits orange to red fluorescence (hereinafter referred to as “orange to red phosphor” as appropriate) include the following. The emission peak wavelength of the orange to red phosphor is suitably in the wavelength range of usually 580 nm or more, preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less. Examples of such orange to red phosphors include europium composed of broken particles having a red fracture surface and emitting red region (Mg, Ca, Sr, Ba) 2 Si 5 N 8 : Eu. The activated alkaline earth silicon nitride-based phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) 2 O 2 S: Examples include europium-activated rare earth oxychalcogenide phosphors represented by Eu. Furthermore, the oxynitride and / or acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A No. 2004-300247 A phosphor containing a sulfide and containing an oxynitride having an alpha sialon structure in which a part or all of the Al element is substituted with a Ga element can also be used in this embodiment. These are phosphors containing oxynitride and / or oxysulfide.

Other red phosphors include Eu-activated oxysulfide phosphors such as (La, Y) 2 O 2 S: Eu, Y (V, P) O 4 : Eu, Y 2 O 3 : Eu, etc. Eu-activated oxide phosphor, (Ba, Sr, Ca, Mg) 2 SiO 4: Eu, Mn, (Ba, Mg) 2 SiO 4: Eu, Eu such as Mn, Mn-activated silicate phosphor, Eu-activated tungstate phosphors such as LiW 2 O 8 : Eu, LiW 2 O 8 : Eu, Sm, Eu 2 W 2 O 9 , Eu 2 W 2 O 9 : Nb, Eu 2 W 2 O 9 : Sm (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO 3 : Eu-activated aluminate phosphors such as Eu, LiY 9 (SiO 4 ) 6 O 2 : Eu, Ca 2 Y 8 (SiO 4 ) 6 O 2 : Eu, (Sr, Ba, Ca) 3 SiO 5 : Eu, Sr 2 Ba-activated silicate phosphors such as BaSiO 5 : Eu, (Y, Gd) 3 Al 5 O 12 : Ce, (Tb, Gd) 3 Al 5 O 12 : Ce-activated aluminate phosphors such as Ce, (Mg, Ca, Sr, Ba ) 2 Si 5 N 8: Eu, (Mg, Ca, Sr, Ba) SiN 2: Eu, (Mg, Ca, Sr, Ba) AlSiN 3: Eu -activated nitride such as Eu Phosphors, Ce-activated nitride phosphors such as (Mg, Ca, Sr, Ba) AlSiN 3 : Ce, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, Mn, etc. Eu, Mn-activated halophosphate phosphor, Ba 3 MgSi 2 O 8 : Eu, Mn, (Ba, Sr, Ca, Mg) 3 (Zn, Mg) Si 2 O 8 : Eu, Mn, etc. activated silicate phosphor, 3.5MgO · 0.5MgF 2 · Ge 2: Mn activated germanate salt phosphors such as Mn, Eu Tsukekatsusan nitride phosphor such as Eu-activated α-sialon, (Gd, Y, Lu, La) 2 O 3: Eu, Bi, etc. Eu, Bi-activated oxide phosphor, (Gd, Y, Lu, La) 2 O 2 S: Eu, Bi-activated oxysulfide phosphor such as Eu, Bi, (Gd, Y, Lu, La) VO 4 : Eu, Bi activated vanadate phosphors such as Eu, Bi, etc., SrY 2 S 4 : Eu, Ce activated sulfide phosphors such as Eu, Ce, etc., Ce activated sulfide fluorescence such as CaLa 2 S 4 : Ce, etc. (Ba, Sr, Ca) MgP 2 O 7 : Eu, Mn, (Sr, Ca, Ba, Mg, Zn) 2 P 2 O 7 : Eu, Mn-activated phosphate phosphors such as Eu and Mn , (Y, Lu) 2 WO 6 : Eu, Mo-activated tungstate phosphor such as Eu, Mo, (Ba, Sr, Ca) x Si y Nz: Eu, Ce (where x, y, z represent an integer of 1 or more. Eu, Ce activated nitride phosphors such as (Ca, Sr, Ba, Mg) 10 (PO 4 ) 6 (F, Cl, Br, OH) 2 : Eu, Mn activated halophosphorus such as Eu, Mn Acid salt phosphor, ((Y, Lu, Gd, Tb) 1-xy Sc x Ce y ) 2 (Ca, Mg) 1-r (Mg, Zn) 2 + r Siz -q Ge q O 12 + δ It is also possible to use a Ce-activated silicate phosphor or the like.

  Examples of red phosphors include β-diketonates, β-diketones, aromatic carboxylic acids, red organic phosphors composed of rare earth element ion complexes having an anion such as Bronsted acid as a ligand, and perylene pigments (for example, Dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), anthraquinone pigment, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, It is also possible to use a cyanine pigment or a dioxazine pigment.

Of the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. Examples of such orange phosphors include Eu-activated silicate phosphors such as (Sr, Ba, Ca) 3 SiO 5 : Eu, Sr 2 BaSiO 5 : Eu, (Sr, Mg) 3 (PO 4 ). 2 : Sn-activated phosphate phosphors such as Sn 2+ and the like.
Any one of the red phosphors exemplified above may be used alone, or two or more may be used in any combination and ratio. Among the above examples, as the red phosphor, (Ca, Sr, Ba) AlSiN 3 : Eu, (Ca, Sr, Ba) AlSiN 3 : Ce, (La, Y) 2 O 2 S: Eu are preferable, (Sr, Ca) AlSiN 3 : Eu and (La, Y) 2 O 2 S: Eu are particularly preferable.
Moreover, among the above examples, (Sr, Ba) 3 SiO 5 : Eu is preferable as the orange phosphor.

[2-1-2-2] Green phosphor
Examples of the base phosphor that emits green fluorescence (hereinafter referred to as “green phosphor” as appropriate) include the following. The emission peak wavelength of the green phosphor is usually in the wavelength range of 490 nm or more, preferably 510 nm or more, more preferably 515 nm or more, and usually 560 nm or less, preferably 540 nm or less, more preferably 535 nm or less. .

As such a green phosphor, for example, a europium-activated alkali represented by (Mg, Ca, Sr, Ba) Si 2 O 2 N 2 : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Europium-activated alkaline earth silicate composed of an earth silicon oxynitride phosphor, broken particles having a fracture surface, and emitting green light (Ba, Ca, Sr, Mg) 2 SiO 4 : Eu System phosphors and the like.

Other green phosphors include Eu-activated aluminate phosphors such as Sr 4 Al 14 O 25 : Eu, (Ba, Sr, Ca) Al 2 O 4 : Eu, and (Sr, Ba) Al 2. Si 2 O 8 : Eu, (Ba, Mg) 2 SiO 4 : Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ba, Sr, Ca) 2 (Mg, Zn) Si 2 O 7 : Eu, (Ba, Ca, Sr, Mg) 9 (Sc, Y, Lu, Gd) 2 (Si, Ge) 6 O 24 : Eu-activated silicate phosphor such as Eu, Y 2 SiO 5 : Ce, Ce, Tb-activated silicate phosphors such as Tb, Sr 2 P 2 O 7 —Sr 2 B 2 O 5 : Eu-activated borate phosphate phosphors such as Eu, Sr 2 Si 3 O 8 -2SrCl 2 : Eu-activated halo silicate phosphor such as Eu, Zn 2 SiO 4: M such as Mn Activated silicate phosphors, CeMgAl 11 O 19: Tb, Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as Tb, Ca 2 Y 8 (SiO 4) 6 O 2: Tb, La 3 Ga 5 SiO 14 : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga 2 S 4 : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, Y 3 (Al, Ga) 5 O 12 : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) 3 (Al, Ga) 5 O 12 : Ce-activated aluminate phosphor such as Ce, Ca 3 Sc 2 Si 3 O 12 : Ce, Ca 3 (Sc, Mg, Na, Li) 2 Si 3 O 12 : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc 2 O 4 : Ce, SrSi 2 O 2 N 2 : Eu, (Mg, Sr, B a, Ca) Si 2 O 2 N 2 : Eu, Eu-activated oxynitride phosphors such as Eu-activated β sialon, BaMgAl 10 O 17 : Eu, Mn-activated aluminate phosphors such as Eu and Mn, Eu-activated aluminate phosphors such as SrAl 2 O 4 : Eu, Tb-activated oxysulfide phosphors such as (La, Gd, Y) 2 O 2 S: Tb, and Ce such as LaPO 4 : Ce, Tb , Tb-activated phosphate phosphors, sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al, (Y, Ga, Lu, Sc, La) BO 3 : Ce, Tb, Na 2 Gd 2 B 2 O 7 : Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6 : Ce, Tb activated borate phosphor such as K, Ce, Tb, Ca 8 Mg ( SiO 4 ) 4 Cl 2 : Eu, Mn activated halosilicate phosphor such as Eu, Mn, ( Sr, Ca, Ba) (Al, Ga, In) 2 S 4 : Eu-activated thioaluminate phosphor such as Eu, thiogallate phosphor, (Ca, Sr) 8 (Mg, Zn) (SiO 4 ) 4 Cl 2 : Eu, Mn activated halosilicate phosphor such as Eu, Mn, etc., MSi 2 O 2 N 2 : Eu, M 3 Si 6 O 9 N 4 : Eu, M 2 Si 7 O 10 N 4 : Eu , M represents an alkaline earth metal element. It is also possible to use Eu-activated oxynitride phosphors such as
In addition, as the green phosphor, it is also possible to use a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a nartaric imide-based fluorescent dye, or an organic phosphor such as a terbium complex. is there.

[2-1-2-3] Blue phosphor
Examples of the base phosphor that emits blue fluorescence (hereinafter referred to as “blue phosphor” as appropriate) include the following. The emission peak wavelength of the blue phosphor is usually in the wavelength range of 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 470 nm or less, more preferably 460 nm or less. .

As such a blue phosphor, a europium-activated barium magnesium aluminate system represented by BaMgAl 10 O 17 : Eu composed of growing particles having a substantially hexagonal shape as a regular crystal growth shape and emitting light in a blue region. Europium activated halo represented by (Ca, Sr, Ba) 5 (PO 4 ) 3 Cl: Eu, which is composed of phosphors and growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a blue region. Calcium phosphate phosphor, composed of growing particles having a substantially cubic shape as a regular crystal growth shape, emits light in the blue region, and is activated by europium represented by (Ca, Sr, Ba) 2 B 5 O 9 Cl: Eu Consists of alkaline earth chloroborate phosphors, fractured particles with fractured surfaces, and light emission in the blue-green region (Sr, Ca, Ba) Al 2 O 4 : Eu or (Sr, Ca, Ba) 4 Al 14 O 25 : Europium activated alkaline earth aluminate-based phosphor represented by Eu.

Other blue phosphors include Sn-activated phosphate phosphors such as Sr 2 P 2 O 7 : Sn, (Sr, Ca, Ba) Al 2 O 4 : Eu or (Sr, Ca, Ba). 4 Al 14 O 25 : Eu, BaMgAl 10 O 17 : Eu, BaAl 8 O 13 : Eu-activated aluminate phosphors such as Eu, SrGa 2 S 4 : Ce, CaGa 2 S 4 : Ce-activated such as Ce Thiogallate phosphor, (Ba, Sr, Ca) MgAl 10 O 17 : Eu, BaMgAl 10 O 17 : Eu-activated aluminate phosphor such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl 10 O 17 : Eu, Mn activated aluminate phosphor such as Eu, Mn, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu, (Ba, Sr, Ca) 5 (PO 4 ) 3 (Cl, F, Br, OH): Eu-activated halophosphate phosphors such as Eu, Mn, Sb, BaAl 2 Si 2 O 8 : Eu, (Sr, Ba) 3 MgSi 2 O 8 : Eu-activated silicic acid such as Eu Salt phosphors, Eu-activated phosphate phosphors such as Sr 2 P 2 O 7 : Eu, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, and Ce-activated such as Y 2 SiO 5 : Ce Silicate phosphor, tungstate phosphor such as CaWO 4 , (Ba, Sr, Ca) BPO 5 : Eu, Mn, (Sr, Ca) 10 (PO 4 ) 6 .nB 2 O 3 : Eu, 2SrO. 0.84P 2 O 5 .0.16B 2 O 3 : Eu, Mn-activated borate phosphate phosphor such as Eu, Eu-activated halosilicate phosphor such as Sr 2 Si 3 O 8 · 2SrCl 2 : Eu Etc. can also be used.

Further, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyrazoline-based, triazole-based fluorescent dyes, organic phosphors such as thulium complexes, and the like can be used. . Among the above examples, as the blue phosphor, BaMgAl 10 O 17 : Eu, (Ba, Ca, Mg) 2 SiO 4 : Eu, (Sr, Ca, Ba, Mg) 10 (PO 4 ) 6 Cl 2 : Eu is preferred, and BaMgAl 10 O 17 : Eu is particularly preferred.

[2-1-2-4] Yellow Phosphor The base phosphor that emits yellow fluorescence (hereinafter, appropriately referred to as “yellow phosphor”) includes the following. The emission peak wavelength of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. .
Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors.

In particular, RE 3 M 5 O 12 : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, and Sc. And M a 3 M b 2 M c 3 O 12 : Ce (where M a is a divalent metal element and M b is a trivalent metal element) , M c represents a tetravalent metal element) garnet phosphor having a garnet structure represented by like, AE 2 M d O 4: . Eu ( where, AE is, Ba, Sr, Ca, Mg , and An orthosilicate phosphor represented by at least one element selected from the group consisting of Zn, M d represents Si and / or Ge, and the like. Acid in which a part of Compound phosphor, AEAlSiN 3: Ce (here, AE is, Ba, Sr, C
a, at least one element selected from the group consisting of Mg and Zn. And phosphors activated with Ce such as nitride-based phosphors having a CaAlSiN 3 structure.

In addition, as yellow phosphors, sulfide-based fluorescence such as CaGa 2 S 4 : Eu, (Ca, Sr) Ga 2 S 4 : Eu, (Ca, Sr) (Ga, Al) 2 S 4 : Eu, etc. It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a SiAlON structure such as a body, Cax (Si, Al) 12 (O, N) 16 : Eu. Examples of yellow phosphors include brilliant sulfoflavine FF (Colour Index Number 56205), basic yellow HG (Colour Index Number 46040), eosine (Colour Index Number 45380), and rhodamine 6G.
It is also possible to use fluorescent dyes such as (Colour Index Number 45160).

[2-1-3] Physical Properties of Substrate Phosphor The particle size of the substrate phosphor used in the phosphor of the present invention is not particularly limited, but the median particle size (D 50 ) is usually 0.1 μm or more, preferably It is 2 μm or more, more preferably 10 μm or more. Moreover, it is 100 micrometers or less normally, Preferably it is 50 micrometers or less, More preferably, it is 25 micrometers or less. If D 50 is too small, and the luminance decreases, there is a possibility that the base phosphor particles tend to aggregate. On the other hand, when D 50 is too large, there is a possibility that clogging of such coating unevenness or dispenser may occur.

  The particle size distribution (QD) of the base phosphor particles is preferably small in order to align the dispersed state of the particles in the phosphor-containing composition. However, in order to reduce the particle size, the classification yield decreases, leading to an increase in cost. Usually, it is 0.03 or more, preferably 0.05 or more, more preferably 0.07 or more. Moreover, it is 0.4 or less normally, Preferably it is 0.3 or less, More preferably, it is 0.2 or less. Further, the shape of the base phosphor particles is not particularly limited.

In the present invention, the median particle size (D 50 ) and particle size distribution (QD) can be obtained from a weight-based particle size distribution curve. The weight-based particle size distribution curve is obtained by measuring the particle size distribution by a laser diffraction / scattering method, and specifically, for example, can be measured as follows.
A phosphor is dispersed in a solvent such as ethylene glycol under an environment of an air temperature of 25 ° C. and a humidity of 70%.
Measurement is performed with a laser diffraction particle size distribution measuring apparatus (Horiba, Ltd. LA-300) in a particle size range of 0.1 μm to 600 μm.
Integrated value in the weight particle size distribution curve is denoted a particle size value when the 50% and median particle diameter D 50. Further, the particle size values when the integrated values are 25% and 75% are expressed as D 25 and D 75 , respectively, and defined as QD = (D 75 −D 25 ) / (D 75 + D 25 ). A small QD means a narrow particle size distribution.

[2-2] Metal Oxide Film [2-2-1] Composition The phosphors of the first and second inventions are metal oxides obtained by hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof. It is covered with an object. The metal alkoxide and its derivative are the same as in [1-1] above.
[2-2-2] Continuity of film The preferred form of the phosphor of the first invention and the phosphor of the second invention are substantially observed by a transmission electron microscope. It is a feature that it is done.
Here, “substantially continuity is observed” means that a state in which the coating almost completely covers the base phosphor is observed. Specifically, it can be confirmed that the film is observed around the base phosphor with no or almost no cut by the following film property observation method using a transmission electron microscope.

[Observation of film properties by transmission electron microscope]
The phosphor is dispersed in ethanol, dropped onto a microgrid (mesh with a perforated carbon film for a transmission electron microscope (TEM)), and dried naturally. The surface state of the phosphor on the microgrid is observed by TEM. The TEM to be used is not particularly limited, but the observation is performed at an accelerating voltage at which electrons cannot pass through the phosphor and the formed film can be observed.

[2-2-3] Film thickness In the preferred form of the phosphor of the first invention and the phosphor of the second invention, the film thickness of the metal oxide film is usually 1 nm or more, preferably 100 nm or more, more preferably. Is 200 nm or more, usually 10,000 nm or less, preferably 5000 nm or less, and more preferably 2000 nm or less. The average film thickness of the metal oxide film is usually 10 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and usually 2000 nm or less, preferably 1500 nm or less, and more preferably 1000 nm or less. If the film thickness is too thick, reflection / absorption of excitation light may occur. If it is too thin, the continuity of the film may be impaired, and the moisture resistance may be insufficient.

In addition, when the average film thickness and the local film thickness are significantly different, that is, when the film thickness unevenness of the phosphor film is large, the large film thickness may be distorted and the film may peel off. It is preferable that the variation in thickness is small and that there is no great difference between the film thickness at each place and the average film thickness.
The film thickness of the metal oxide film can be obtained by measuring the film thickness observed by the film property observation method using the transmission electron microscope described above. The average film thickness can be obtained from the average value of the film portion by image analysis of the transmission electron micrograph described above.

[2-2-4] Moisture absorption increase rate The preferred embodiment of the phosphor of the first invention and the phosphor of the second invention are metals measured by a moisture absorption measurement test according to the following (i) to (iii): It is characterized in that the moisture absorption increase rate of the oxide film is 5% by weight or less.
[Moisture absorption measurement test]
(I) The film is formed on the orange phosphor Sr 2 BaSiO 5 : Eu (hereinafter abbreviated as SBS, D50 = 20 ± 3 μm).
(Ii) Leave in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 100 hours.
(Iii) Moisture absorption increase rate (% by weight) = (weight after moisture absorption test−weight before moisture absorption test) / (weight before moisture absorption test) × 100.
The moisture absorption increase rate is preferably 5% by weight or less, and more preferably 3% by weight or less. Moreover, it is 1 weight% or more normally. If the moisture absorption rate is too high, the effect of suppressing moisture absorption on the base phosphor is weak and long-term weather resistance cannot be obtained.

[2-2-5] Coating amount of metal oxide The coating amount of the metal oxide of the phosphor of the present invention varies depending on the physical properties of the substrate phosphor, but is usually 1% by weight or more based on the substrate phosphor, preferably Is 5% by weight or more, more preferably 10% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. If the coating amount is too small, the continuity of the film may be impaired and the moisture resistance may be insufficient. If the coating amount is too large, excitation light may be reflected or absorbed.

[2-2-6] Dispersibility The phosphor of the present invention has excellent dispersibility. The dispersibility of the phosphor can be confirmed by sufficiently dispersing it in a liquid medium constituting the phosphor-containing composition described later, and then allowing it to stand and measuring the production rate of a transparent supernatant layer.
When encapsulating a large number of semiconductor light emitting devices with the phosphor-containing composition of the present invention described later, the phosphor of the present invention is not subjected to this test because it does not cause a change in quality between the product in the initial stage of the sealing process and the product in the final stage. As a result, the slower the sedimentation rate, the better. It is preferable that a colorless and transparent supernatant layer is not seen on the liquid surface after standing for 6 hours, and it is further more preferable that a colorless and transparent supernatant layer is not seen even after standing for 10 hours.

However, when the viscosity of the liquid medium is high and measurement takes time, this test can be replaced with another liquid medium having a similar skeleton. For example, when a silicone resin is used as the liquid medium, the dispersibility can be evaluated using a silicone oil as an alternative. The phosphor of the present invention may have a feature that the sedimentation rate in the phosphor-containing composition made of the sealing resin is lower than that of the base phosphor on which the metal oxide film is not formed. The reason for this is not necessarily clear, but the average specific gravity of the phosphor particles is reduced by being covered with a metal oxide film having a small specific gravity, and the resistance to sedimentation motion in a viscous liquid is caused by the unevenness of the surface film, Etc. are estimated.
In addition, when a silicone resin is used as the sealing resin and a silica film is used as the metal oxide film, the wettability between silicone and silica is good, so that the effect of improving the dispersibility of the silica-coated phosphor is also expected.

[3] Phosphor-containing composition It is essential that the phosphor-containing composition of the present invention contains the phosphor of the present invention.
The phosphor-containing composition of the present invention is configured to contain a liquid medium and other optional components as described below, for example.

[3-1] Liquid medium As the liquid medium to be used, an organic material and an inorganic material can be used.
Examples of organic materials include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins. In particular, when a high-power light-emitting device such as illumination is required, it is preferable to use a silicon-containing compound for the purpose of heat resistance and light resistance.
A silicon-containing compound is a compound having a silicon atom in the molecule, organic materials such as polyorganosiloxane (silicone-based materials), inorganic materials such as silicon oxide, silicon nitride, and silicon oxynitride, and borosilicates and phosphosilicates. Examples thereof include glass materials such as salts and alkali silicates. Among these, silicone materials are preferable from the viewpoint of ease of handling.

[3-1-1] Silicone-based material The silicone-based material usually refers to an organic polymer having a siloxane bond as a main chain. For example, a compound represented by the general composition formula (1) and / or a mixture thereof is used. Can be mentioned.
(R 1 R 2 R 3 SiO 1/2 ) M (R 4 R 5 SiO 2/2 ) D (R 6 SiO 3/2 ) T (SiO 4/2 ) Q
... Formula (1)
Here, R 1 to R 6 may be the same or different and are selected from the group consisting of an organic functional group, a hydroxyl group, and a hydrogen atom. M, D, T, and Q are 0 to less than 1 and satisfy M + D + T + Q = 1.
When a silicone material is used for sealing a semiconductor light emitting element, it can be used after being sealed with a liquid silicone material and then cured by heat or light.

[3-1-2] Types of silicone-based materials Silicone-based materials such as addition polymerization curing type, condensation polymerization curing type, ultraviolet curing type, peroxide vulcanization type and the like are usually classified when silicone materials are classified according to the curing mechanism. be able to. Among these, addition polymerization curing type (addition type silicone resin), condensation curing type (condensation type silicone resin), and ultraviolet curing type are preferable. Hereinafter, the addition type silicone material and the condensation type silicone material will be described.

[3-1-2-1] Addition type silicone material The addition type silicone material refers to a polyorganosiloxane chain crosslinked by an organic addition bond. A typical example is a compound having a Si—C—C—Si bond at a crosslinking point obtained by reacting vinylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst. As these, commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd.

[3-1-2-2] Condensation type silicone material Examples of the condensation type silicone material include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. be able to.
Specific examples include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (1) and / or (2) and / or oligomers thereof.

(In the formula (1), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y 1 represents a monovalent organic group. M represents one or more integers representing the valence of M, and n represents one or more integers representing the number of X groups, provided that m ≧ n.

(In the formula (2),
M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, Y 1 represents a monovalent organic group, and Y 2 represents u. Represents an organic group having a valence, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, and u represents an integer of 2 or more. )
Moreover, as a curing catalyst, a metal chelate compound etc. can be used suitably, for example. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr.
As such a condensation type silicone material, for example, semiconductor light emitting device members described in Japanese Patent Application Nos. 2006-47274 to 47277 and Japanese Patent Application No. 2006-176468 are suitable.
Examples of the inorganic material in the liquid medium used include metal alkoxides,
Examples include a solution obtained by hydrolytic polymerization of a solution containing a ceramic precursor polymer or metal alkoxide by a sol-gel method, or an inorganic material obtained by solidifying a combination thereof (for example, an inorganic material having a siloxane bond). it can.

[3-2] Other components In addition to the above components, the phosphor-containing composition of the present invention comprises a curing agent, a curing accelerator, a curing catalyst, a polymerization inhibitor, a dye, an antioxidant, a stabilizer (phosphorus-based). Processing stabilizers such as processing stabilizers, oxidation stabilizers, heat stabilizers, light-resistant stabilizers such as UV absorbers, etc.), silane coupling agents, light diffusing materials, phosphors not dependent on the present invention Any of the additives known in the art such as fillers can be used.

[3-3] Method for Producing Phosphor-Containing Composition The method for producing the phosphor-containing composition of the present invention is not particularly limited, and the phosphor of the present invention and additives to be added as necessary are contained in the liquid medium. Any method that uniformly disperses may be used.
Examples of a method for uniformly dispersing in a liquid resin include a conventionally known method and an improved method thereof. Specifically, the following method is mentioned, for example. That is, a liquid resin, a phosphor, a filler such as silica fine particles, a crosslinking agent, a curing catalyst, and other additives can be blended and mixed by a mixer, a high-speed disper, a homogenizer, a three-roll, a kneader or the like. In this case, a liquid resin composition can be produced in the form of one liquid by mixing all the components. In addition, two liquids of (i) a liquid composition mainly composed of a liquid resin and a phosphor and (ii) a crosslinking agent liquid mainly composed of a crosslinking agent and a curing catalyst are prepared, and the resin composition is prepared immediately before use. The final liquid resin composition may be produced by mixing the product and the crosslinking agent solution.

  The amount of the phosphor of the present invention is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and more preferably 1 part by weight or more with respect to 100 parts by weight of the liquid resin. Moreover, it is 100 parts weight or less normally, Preferably it is 80 parts weight or less, More preferably, it is 60 parts weight or less. If the blending amount of the phosphor is too small, the light emission amount of the desired color is insufficient, and if it is too large, the cost is increased and this is disadvantageous in terms of economy.

[3-4] Physical Properties of Phosphor-Containing Composition [3-4-1] Viscosity The viscosity of the phosphor-containing composition of the present invention is usually 500 mPa · s or more, preferably 1000 mPa · s or more, more preferably 2000 mPa · s. s or more, usually 15000 mPa · s or less, 10000 mPa · s or less, preferably 8000 mPa · s or less. If the viscosity is too high, it may cause trouble such as blockage of pipes at the time of injection, and bubbles may be difficult to escape, and further, lead wires of semiconductor elements are likely to be disconnected. On the other hand, if the viscosity is too low, the phosphor particles settle, which is not preferable.

[3-4-2] Curing When the phosphor-containing composition of the present invention is in a liquid state as described above, the liquid composition is injected, filled, dropped, applied, etc. on a substrate on which a semiconductor light emitting element or the like is disposed. After the light emitting device is covered with a liquid composition by heating, the composition is cured by heating, light irradiation, humidification, etc., so that the light emitting device can be sealed with a solid-state phosphor-containing sealing layer. .
In addition, after the liquid phosphor-containing composition is first cured and molded into a film or sheet, the light emitting element can be sealed by placing the composition so as to cover the light emitting element.
When the cured product of the phosphor-containing composition is exposed to a high heat of, for example, 260 ° C. in a solder reflow test, or when a high temperature of, for example, 100 ° C. and a low temperature of −50 ° C. are reciprocated in a temperature cycle test, There is a risk that the separation efficiency between the resin and the fluorescence emitted by the phosphor may be impaired, but when using a silicone resin as the sealing resin in the present invention and the phosphor surface film is a silica film, Because the silicone resin and the silica film are well-matched, the occurrence of interfacial delamination is suppressed compared to the case of using a phosphor without a surface film, and the phosphor-containing sealing layer has excellent solder reflow resistance and temperature cycle resistance. Is expected to be.

[4] Light-emitting device The light-emitting device of the present invention is formed by a known method using the phosphor-containing composition described in [3]. Hereinafter, the light emitting device of the present invention will be described.
[4-1] Light source The light source in the light emitting device of the present invention emits light that excites the phosphor of [2]. The light emission wavelength of the light source is not particularly limited as long as it overlaps with the absorption wavelength of the light emitter, and a light emitter in a wide light emission wavelength region can be used. Usually, an illuminant having an emission wavelength from the near ultraviolet region to the blue region is used, and the specific numerical value is usually 300 nm or more, preferably 330 nm or more, and usually 500 nm or less, preferably 480 nm or less. A light emitter having the following is used. As this light source, a semiconductor light emitting element is generally used, and specifically, a light emitting diode (LED), a semiconductor laser diode (LD), or the like can be used.

  Among these, as the light source, a GaN LED or LD using a GaN compound semiconductor is preferable. This is because GaN-based LEDs and LDs have significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and are extremely bright with very low power when combined with the phosphor. This is because light emission can be obtained. For example, for the same current load, a GaN-based LED or LD usually has a light emission intensity 100 times or more that of a SiC-based. A GaN-based LED or LD preferably has an Al x Gay N light emitting layer, a GaN light emitting layer, or an In x Gay N light emitting layer. Among GaN-based LEDs, those having an InxGayN light-emitting layer are particularly preferred because the emission intensity is very strong, and in GaN-based LDs, those having a multiple quantum well structure of an InxGayN layer and a GaN layer have an emission intensity. It is particularly preferred because it is very strong.

In the above, the value of x + y is usually in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light emitting layer, p layer, n layer, electrode, and substrate as basic components, and the light emitting layer is sandwiched between n-type and p-type AlxGayN layers, GaN layers, or InxGayN layers. Those having the heterostructure are preferably high in luminous efficiency, and those having a heterostructure in the quantum well structure are further preferable because of higher luminous efficiency.

[4-2] Selection of phosphor In the light emitting device of the present invention, the phosphors described above (the red phosphor, the green phosphor, the blue phosphor, etc. according to the present invention, and the phosphor not depending on the present invention if necessary) Etc.) may be appropriately selected depending on the use of the light emitting device.
When the light emitting device of the present invention is configured as a white light emitting device, one or more phosphors may be appropriately combined so that desired white light is obtained. When a blue light emitting element is used as a light source, it is preferable to use a yellow phosphor having a complementary color relationship of blue as a phosphor, and red and green phosphors to obtain white with higher color rendering properties. When using a semiconductor light emitting device that emits near-ultraviolet light, phosphors of three colors of red, green, and blue are preferably used.

Specifically, when the light-emitting device of the present invention is configured as a white light-emitting device, examples of preferable combinations of the light source and the phosphor include the following combinations (i) to (iii).
(I) A blue light emitter (blue LED or the like) is used as a light source, and a red phosphor and a green phosphor are used as phosphors.
(Ii) A near-ultraviolet light emitter (near-ultraviolet LED or the like) is used as a light source, and a red phosphor, a green phosphor and a blue phosphor are used in combination as phosphors.
(Iii) A blue light emitter (blue LED or the like) is used as a light source, and an orange phosphor and a green phosphor are used.

[4-3] Configuration of Light-Emitting Device The light-emitting device of the present invention is only required to include the above-described light source and the phosphor-containing composition of the present invention, and other configurations are not particularly limited. The above-mentioned light source and phosphor-containing composition are arranged on the top. When the phosphor-containing composition is in a liquid state, the liquid phosphor composition is injected, filled, dripped, and applied to the substrate on which the light source is disposed, and then the composition is cured by heating or light irradiation, thereby producing a light source It can be set as the structure sealed with hardened | cured material. When the phosphor-containing composition is a solid phase, a structure in which the light source is sealed can be obtained by forming it into a film or a sheet and covering the light source. At this time, the phosphor is excited by the light emission of the light source to generate light emission, and the light emission of the light source and / or the light emission of the phosphor is arranged to be taken out to the outside. In this case, the red phosphor does not necessarily have to be mixed in the same layer as the green phosphor and the blue phosphor. For example, the blue phosphor and the green phosphor are placed on the layer containing the red phosphor. The layer to contain may be laminated | stacked.

[4-4] Embodiments of Light-Emitting Device Hereinafter, the light-emitting device of the present invention will be described in more detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Any modifications can be made without departing from the scope of the present invention.
FIG. 1 is a diagram schematically showing a configuration of a light emitting device according to an embodiment of the present invention. The light emitting device 1 of the present embodiment includes a frame 2, a blue LED 3 that is a light source, and a phosphor-containing portion 4 that absorbs part of light emitted from the blue LED 3 and emits light having a wavelength different from that.
The frame 2 is a metal base for holding the blue LED 3 and the phosphor-containing portion 4. On the upper surface of the frame 2, a trapezoidal concave section (dent) 2A having an opening on the upper side in FIG. Thereby, since the frame 2 has a cup shape, the light emitted from the light emitting device 1 can have directivity, and the emitted light can be used effectively. Further, the inner surface of the concave portion 2A of the frame 2 is enhanced in the reflectance of light in the entire visible light region by metal plating such as silver, so that the light hitting the inner surface of the concave portion 2A of the frame 2 can also be emitted. Can be discharged in a predetermined direction.

  A blue LED 3 is installed as a light source at the bottom of the recess 2 </ b> A of the frame 2. The blue LED 3 is an LED that emits blue light when supplied with electric power. Part of the blue light emitted from the blue LED 3 is absorbed as excitation light by the luminescent material (phosphor) in the phosphor-containing portion 4, and another part is directed from the light emitting device 1 in a predetermined direction. To be released.

  The blue LED 3 is installed at the bottom of the recess 2A of the frame 2 as described above. Here, the frame 2 and the blue LED 3 are bonded by a silver paste (a mixture of silver particles in an adhesive) 5. Thus, the blue LED 3 is installed on the frame 2. Further, the silver paste 5 also plays a role of efficiently radiating heat generated in the blue LED 3 to the frame 2.

Further, a gold wire 6 for supplying power to the blue LED 3 is attached to the frame 2. That is, the electrode (not shown) provided on the upper surface of the blue LED 3 is connected by wire bonding using the wire 6, and when the wire 6 is energized, power is supplied to the blue LED 3. It emits blue light. One or a plurality of wires 6 are attached in accordance with the structure of the blue LED 3.

  Further, the concave portion 2A of the frame 2 is provided with a phosphor-containing portion 4 that absorbs part of the light emitted from the blue LED 3 and emits light having a different wavelength. The phosphor-containing part 4 is formed of the phosphor-containing composition of the present invention. The phosphor is a substance that is excited by blue light emitted from the blue LED 3 and emits light having a wavelength longer than that of the blue light. The phosphor constituting the phosphor-containing portion 4 may be a single type or a mixture of a plurality, and the sum of the light emitted from the blue LED 3 and the light emitted from the phosphor light-emitting portion 4 is a desired color. Choose to be. The color is not limited to white, but may be yellow, orange, pink, purple, blue-green, or the like. Further, it may be an intermediate color between these colors and white.

The mold unit 7 functions as a lens for protecting the blue LED 3, the phosphor-containing unit 4, the wire 6 and the like from the outside and controlling the light distribution characteristics. An epoxy resin can be mainly used for the mold part 7.
FIG. 2 is a schematic cross-sectional view showing an embodiment of a surface emitting illumination device incorporating the light emitting device 1 shown in FIG. In FIG. 2, 8 is a surface emitting illumination device, 9 is a diffusion plate, and 10 is a holding case.

This surface-emitting illuminating device 8 has a large number of light-emitting devices 1 on the bottom surface of a rectangular holding case 10 whose inner surface is light-opaque such as a white smooth surface, and a power source for driving the light-emitting device 1 on the outside thereof. And a circuit or the like (not shown). In order to make the light emission uniform, a diffusion plate 9 such as an acrylic plate made of milky white is fixed to a portion corresponding to the lid portion of the holding case 10.
Then, the surface-emitting illumination device 8 is driven to apply blue voltage to the blue LED 3 of the light-emitting device 1 to emit blue light or the like. Part of the emitted light is absorbed in the phosphor-containing portion 4 by the phosphor of the present invention, which is a wavelength conversion material, and another phosphor added as necessary, and converted into light having a longer wavelength. Light emission with high luminance is obtained by mixing with blue light or the like that has not been absorbed. This light passes through the diffusion plate 9 and is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 9 of the holding case 10.

  In the light-emitting device of the present invention, in particular, when a surface-emitting type is used as the excitation light source, it is preferable that the phosphor-containing portion is formed into a film. That is, since the cross-sectional area of the light from the surface-emitting type phosphor is sufficiently large, when the phosphor-containing portion is formed into a film shape in the direction of the cross-section, the irradiation cross-section area of the phosphor from the first phosphor is fluorescent. Since it becomes large per body unit quantity, the intensity | strength of light emission from fluorescent substance can be enlarged more.

  In addition, when a surface-emitting type light source is used as the light source and a film-like one is used as the phosphor-containing portion, it is preferable that the light-emitting surface of the light source is directly in contact with the film-like phosphor-containing portion. . Contact here means creating a state where the light source and the phosphor-containing portion are in perfect contact with each other without air or gas. As a result, it is possible to avoid a light amount loss in which light from the light source is reflected by the film surface of the phosphor-containing portion and oozes out, so that the light emission efficiency of the entire apparatus can be improved.

FIG. 3 is a schematic perspective view showing an example of a light-emitting device using a surface-emitting type light source as the light source and applying a film-like one as the phosphor-containing portion. In FIG. 3, 11 is a film-like phosphor-containing portion having the phosphor, 12 is a surface-emitting GaN-based LD as a light source, and 13 is a substrate. In order to create a state where they are in contact with each other, the LD of the light source 12 and the phosphor-containing portion 11 may be formed separately, and their surfaces may be brought into contact with each other by an adhesive or other means. The phosphor-containing portion 11 may be formed (molded) on the light emitting surface. As a result, the light source 12 and the second phosphor-containing portion 11 can be brought into contact with each other.

[4-5] Use of light-emitting device The light-emitting device of the present invention can emit light of various colors depending on the type and amount of the phosphor used, but for lighting use, a light-emitting device that emits white light is useful. When the light emitting device of the present invention emits white light, the luminous efficiency (JISZ8113) is usually 20 lm / W or higher, preferably 22 lm / W or higher, more preferably 25 lm / W or higher, and particularly preferably 28 lm / W. The average color rendering index (JIS Z8726) Ra is 80 or more, preferably 85 or more, more preferably 88 or more.

  The application of the light-emitting device of the present invention is not particularly limited, and can be used in various fields where a normal light-emitting device is used. Moreover, you may use individually or in combination. Specifically, for example, it can be used as a light source for illumination lamps, backlights for liquid crystal panels, various illumination devices such as ultra-thin illumination, and image display devices. In addition, when using the light-emitting device of this invention as a light source of an image display apparatus, you may use together with a color filter.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[1] Surface treatment method [1-1] Material used An orange phosphor Sr 2 BaSiO 5 : Eu (D50 = 21 μm) (hereinafter referred to as “SBS”) was used as a base phosphor to be surface-treated. In this phosphor, SrCO 3 , BaCO 3 , SiO 2 , Eu 2 O 3 are weighed as raw material compounds so as to have a ratio of Sr: Ba: Si: Eu = 1.98: 1: 1: 0.02. After crushing and mixing with ethanol in an agate mortar and evaporating and removing ethanol, the resulting mixture is molded into tablets and heated at 1450 ° C. for 6 hours in a nitrogen atmosphere mixed with 3% hydrogen on a molybdenum foil. To obtain a powder by subsequent pulverization.
Tetraethoxysilane (hereinafter referred to as “TEOS”) manufactured by Tokyo Chemical Industry Co., Ltd., having a purity of 95% or more was used.
Ethanol was manufactured by Kishida Chemical Co., Ltd. and a special grade purity of 99.5% was used.
Ammonia water was manufactured by Kishida Chemical Co., Ltd., and had a special grade purity of 28%.

[1-2] Surface treatment operation (Examples 1 and 2 and Comparative Examples 1 and 2)
[1-2-1] Example 1 (Surface treatment was performed at a temperature of 5 ° C.)
TEOS was used as the metal alkoxide.
In a 500 mL flask, 50 g of TEOS and 224 g of ethanol were added and mixed uniformly to prepare a metal alkoxide solution (TAOM solution).
In a 1L separable flask with a jacket, ethanol 310g, ammonia water 1
After adding 00 g and mixing uniformly, 50 g of SBS powder was added to prepare a substrate phosphor-containing solution (PHOS solution).

A temperature-controlled cooling water is allowed to flow through the jacket of the separable flask to keep the temperature of the reaction solution constant at 5 ° C., and the PHOS solution is vigorously stirred with a stirring blade equipped with a motor so that the SBS powder does not settle. While raising the powder, the TAOM solution was added dropwise over about 4 hours with a metering pump.
After completion of the dropwise addition of the TAOM solution, the reaction solution was allowed to stand and the orange phosphor settled, and then the liquid phase clouded with silica fine particles was removed by decantation. Thereafter, 500 mL of ethanol was added, and the mixture was lightly stirred and allowed to stand, and the liquid layer with white turbidity was removed by decantation. This ethanol washing was repeated four times until the liquid layer became colorless and transparent. The separable flask was dried under reduced pressure at 50 ° C. for 30 minutes, and then dried under reduced pressure at 150 ° C. for 2 hours. A phosphor powder was obtained.

[1-2-2] Example 2 (surface treatment was performed at a temperature of 15 ° C.)
Surface treatment of SBS was performed in the same manner as in Example 1 except that the temperature of the reaction solution was 15 ° C.
[1-2-3] Example 3 (surface treatment at a temperature of 5 ° C. was performed twice)
The surface treatment operation of Example 1 was performed again using the surface-treated SBS phosphor produced in Example 1 as a raw material.
[1-2-4] Comparative Example 1 (SBS was not subjected to surface treatment.)
The substrate SBS phosphor was not subjected to surface treatment and was subjected to the test as it was.
[1-2-5] Comparative Example 2 (Surface treatment was performed at a temperature of 25 ° C.)
Surface treatment of SBS was performed in the same manner as in Example 1 except that the temperature of the reaction solution was 25 ° C.

[2] Property Test Method Examples 1, 2, and 3 and Comparative Examples 1 and 2 were subjected to the following analysis and evaluation.
[2-1] Observation with Transmission Electron Microscope The phosphor was dispersed in ethanol, dropped onto a microgrid (mesh with a perforated carbon film for transmission electron microscope (TEM)), and dried naturally. Using TEM (“H-9000UHR” manufactured by Hitachi, Ltd.), observation was performed at an acceleration voltage of 300 kV.
The results are shown in Table 1.
FIG. 4 shows a TEM photograph of Example 3, and FIG. 5 shows a TEM photograph of Comparative Example 2.
For reference, FIG. 6 shows a scanning electron microscope (SEM) photograph of Example 3 and FIG. 7 of Comparative Example 2.
[2-2] Phosphor Hygroscopic Test The phosphors of Examples 1, 2, 3 and Comparative Examples 1 and 2 were held at 60 ° C. and 90% relative humidity, and the weight increase of the phosphor after a predetermined time was measured.
The results are shown in Table 1.

[3] Results From the results shown in Table 1, the following became clear.
(A) A metal oxide film having a layer in which continuity is substantially observed by a method using a transmission electron microscope, having a thickness of 1 nm or more and 10,000 nm or less, and hydrolyzing a metal alkoxide. Further, it was found that the moisture absorption rate of the phosphor having a film whose moisture absorption increase rate measured by the moisture absorption measurement test according to the following (i) to (iii) is 5% by weight or less is small.

[Moisture absorption measurement test]
(I) The film is formed on the orange phosphor Sr 2 BaSiO 5 : Eu (hereinafter abbreviated as SBS; weight median diameter D50 = 20 ± 3 μm).
(Ii) Leave in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 100 hours.
(Iii) Moisture absorption increase rate (% by weight) = (weight after moisture absorption test−weight before moisture absorption test) / (weight before moisture absorption test) × 100.
(B) It was found that the phosphor obtained by the phosphor surface treatment method including the step of hydrolyzing the metal alkoxide at 0 ° C. or more and 20 ° C. or less has a low moisture absorption rate.
(C) It was found that the phosphor obtained by the phosphor surface treatment method including the step of hydrolyzing the metal alkoxide twice or more has a low moisture absorption rate.

The phosphor surface treatment method and the phosphor of the present invention have extremely high industrial applicability in that they exhibit excellent effects in the following respects.
(I) It is possible to further improve the weather resistance such as moisture resistance of the phosphor before the surface treatment (hereinafter also referred to as a base phosphor) which is the base of the phosphor of the present invention.
(Ii) Dispersibility of the phosphor-containing resin portion of the light-emitting device in the resin can be improved as compared with the base phosphor.

  Moreover, since the phosphor-containing composition, the light-emitting device, the image display device, and the lighting device of the present invention use the phosphor, it has excellent long-term light resistance and high quality. Industrial applicability is extremely high.

It is typical sectional drawing which shows one Example of the light-emitting device of this invention. It is typical sectional drawing which shows an example of the surface emitting illumination apparatus using the light-emitting device of this invention. It is a typical perspective view which shows other embodiment of the light-emitting device of this invention. It is a transmission electron micrograph of the fluorescent substance which performed the surface treatment of this invention. It is the transmission electron micrograph of the fluorescent substance which performed the surface treatment different from this invention. It is a scanning electron micrograph of the fluorescent substance which performed the surface treatment of this invention. It is the scanning electron micrograph of the fluorescent substance which performed the surface treatment different from this invention.

Explanation of symbols

1 Light-emitting device
2 frames
2A Concave part of the frame
3 Blue LED (first light emitter)
4 Phosphor-containing part (second light emitter)
5 Silver paste
6 wires
7 Mold part
8 Surface emitting lighting device
9 Diffusion plate
10 Holding case
11 Phosphor content part
12 Light source
13 Substrate

Claims (8)

  1.   A phosphor surface treatment method comprising a step of hydrolyzing and dehydrating a metal alkoxide and / or a derivative thereof at an atmospheric temperature of 0 ° C. to 20 ° C.
  2.   A phosphor surface treatment method comprising a step of hydrolyzing and dehydrating and polymerizing a metal alkoxide and / or a derivative thereof twice or more.
  3.   A phosphor surface-treated by the phosphor surface treatment method according to claim 1.
  4. A phosphor having a metal oxide film, wherein the metal oxide film satisfies the following conditions (1) to (4).
    (1) It is formed by hydrolysis and dehydration polymerization of a metal alkoxide and / or its derivative. (2) Substantially continuity is observed by a transmission electron microscope.
    (3) The film thickness is 1 nm or more and 10,000 nm or less. (4) The moisture absorption increase rate measured by the moisture absorption measurement test according to the following (i) to (iii) is 5% by weight or less [Moisture absorption measurement test].
    (I) The metal oxide film is formed on the orange phosphor Sr 2 BaSiO 5 : Eu (hereinafter abbreviated as SBS, weight median diameter D50 = 20 ± 3 μm) by an arbitrary method.
    (Ii) Leave in an atmosphere at a temperature of 60 ° C. and a relative humidity of 90% for 100 hours.
    (Iii) Moisture absorption increase rate (% by weight) = (weight after moisture absorption test−weight before moisture absorption test) / (weight before moisture absorption test) × 100.
  5.   A phosphor-containing composition containing the phosphor according to claim 3 or 4.
  6.   A light emitting device using the phosphor according to claim 3 or 4.
  7.   An image display device using the light emitting device according to claim 6.
  8.   An illumination device using the light emitting device according to claim 6.
JP2006296239A 2006-10-31 2006-10-31 Method of surface-treating fluorescent substance, fluorescent substance, fluorescent substance-containing composition, light emitting device, image display device, and illuminating device Pending JP2008111080A (en)

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